Techniques and methods for the determination of haloacetic acids in potable water

Haloethanoic (haloacetic) acids (HAAs) are formed as disinfection byproducts (DBPs) during the chlorination of natural water to make it fit for consumption. Sundry analytical techniques have been applied in order to determine the concentrations of the HAAs in potable water supplies: gas chromatography (GC-MS, GC-ECD); capillary electrophoresis (CE); liquid chromatography (LC), including ion chromatography (IC); and electrospray ionization mass spectrometry (ESI-MS). Detection limits required to analyze potable water samples can be regularly achieved only by GC-ECD and ESI-MS. Without improvements in preconcentration or detector sensitivity, CE and LC will not find application to potable water supplies. The predominant GC-ECD methods use either diazomethane or acidified methanol to esterify (methylate) the carboxylic acid moiety. For HAA5 analytes, regulated under the EPA's Stage 1 DBP Rule, diazomethane is satisfactory. For HAA9 data gathered under the Information Collection Rule, acidified methanol outperforms diazomethane, which suffers from photo-promoted side reactions, especially for the brominated trihaloacetic acids. Although ESI-MS can meet sensitivity and selectivity requirements, limited instrumentation availability means this technique will not be widely used for the time being. However, ESI-MS can provide valuable confirmatory information when coupled with GC-ECD in a research setting.     

离子色谱法测定水中主要阳离子

报导了水中阳离子Ｌｉ＾＋，Ｎａ＾＋，Ｋ＾＋，Ｃａ＾２＋〉Ｍｇ＾２＋的离子色谱分析及其分析精密度，准确性和线性范围。与阴离子组分同时测定用于水中离子总量的分析，获得满意结果。     

Arsenic Speciation Analysis in Water Samples: A Review of The Hyphenated Techniques

Interests in the determination of different arsenic species in natural waters is caused by the fact that toxic effects of arsenic are connected with its chemical forms and oxidation states. In determinations of water samples inorganic arsenate (As(III), As(V)), methylated metabolities (MMAA, DMAA) and other organic forms such as AsB, AsC, arsenosugars or arsenic containing lipids have the most importance. This article provides information about occurrence of the dominant arsenic forms in various water environments. The main factors controlling arsenic speciation in water are described. The quantification of species is difficult because the concentrations of different forms in water samples are relatively lowcompared to the detection limits of the available analytical techniques. Several hyphenated methods used in arsenic speciation analysis are described. Specific advantages and disadvantages of methods can define their application for a particular sample analysis. Insufficient selectivity and sensitivity of arsenic speciation methods cause searching for a new or modifications already existing techniques. Some aspects of improvement and modifications of the methods are highlighted.     

质谱及其联用技术在水中消毒副产物识别和分析中的应用

水中消毒副产物(DBPs)是在水消毒过程中消毒剂与水中溶解性有机物以及无机离子发生反应而产生,其对水环境生态安全和人体健康有不利影响。简述了DBPs的生成、种类、毒性和分析方法等,重点综述了气相色谱-质谱联用(GC-MS)、液相色谱-质谱联用(LC-MS)、离子色谱-质谱联用(IC-MS)以及超高分辨率质谱(UPMS)等质谱(MS)及其联用技术在水中DBPs识别和分析中的应用,分析了不同MS技术的特点和应用实例,提出了MS技术在DBPs研究领域的发展方向与挑战。     

水质丁基黄原酸测定难点探讨

丁基黄原酸是水质监测的重要项目之一。水中丁基黄原酸的测定,在样品采集保存、前处理及仪器分析各阶段都存在一定的技术难点。实际分析时很容易出现测定结果不理想,甚至定性定量错误等问题。结合实验对丁基黄原酸测定中容易出现的问题及注意事项进行探讨,正确区分丁基黄原酸及其盐,有效保存样品,采用低损失的前处理方法以及选择性好的分析仪器,有利于提高丁基黄原酸测定的准确性。众多丁基黄原酸测定方法中,液相色谱质谱法、离子色谱法以及液相色谱法在选择性和灵敏度方面更具优势,也可用于其他方法检出丁基黄原酸时对测定进行确认。     

Bromate analysis in groundwater and wastewater samples

Bromate (BrO(3)(-)) is a disinfection by-product formed during ozonation of potable water supplies containing bromide (Br(-)). Bromate has been classed by the World Health Organisation as a 'possible human carcinogen', leading to implementation of 10-25 microg L(-1)(as BrO(3)(-)) drinking water limits in legislative areas including the United States and European Union. Techniques have been developed for bromate analysis at and below regulatory limits, with Ion Chromatography (IC) coupled with conductivity detection (IC-CD), post-column reaction and ultra-violet (UV) detection (IC-PCR), or inductively coupled plasma-mass spectrometry detection (IC-ICPMS) in widespread use. The recent discovery of bromate groundwater contamination in a UK aquifer has led to a requirement for analysis of bromate in a groundwater matrix, for environmental monitoring and development of remediation strategies. The possibility of bromate-contaminated water discharge into sewage treatment processes, whether accidental or as a pump-and-treat strategy, also required bromate analysis of wastewater sources. This paper summarises techniques currently available for trace bromate analysis in potable water systems and details studies to identify a methodology for routine analysis of groundwater and wastewater samples. Strategies compared were high performance liquid chromatography (HPLC) with direct UV or PCR/UV detection, IC-CD, IC-PCR, and a simple spectrophotometric technique. IC-CD was the most cost-effective solution for simultaneous analysis of bromate and bromide within groundwater samples, having a 5 microg L(-1) detection limit of both anions with limited interference from closely-eluting species. Wastewater samples were successfully analysed for bromate only using HPLC with PCR/UV detection, with detection limits below 20 microg L(-1)(as BrO(3)(-)) and low interference. HPLC with direct UV detection was unsuitable for bromate analysis within the concentration range 50-5000 microg L(-1) which was required for this project, but column choice was shown to be a major factor in determining limits of detection. Spectrophotometry could not reproducibly determine bromate concentration, although the technique showed promise as a quick field method for high-level groundwater bromate analysis.     

Simplification and validation of a large volume polyurethane foam sampler for the analysis of persistent hydrophobic compounds in drinking water

The use of a large volume polyurethane foam (PUF) sampler was validated for rapid extraction of persistent organic pollutants (POPs), such as polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), in raw water and treated water from drinking water plants. To validate the recovery of target compounds in the sampling process, a (37)Cl-labeled standard was spiked into the 1st PUF plug prior to filtration. An accelerated solvent extraction method, as a pressurized liquid extractor (PLE), was optimized to extract the PUF plug. For sample preparation, tandem column chromatography (TCC) clean-up was used for rapid analysis. The recoveries of labeled compounds in the analytical method were 80-110% (n = 9). The optimized PUF-PLE-TCC method was applied in the analysis of raw water and treated potable water from seven drinking water plants in South Korea. The sample volume used was between 18 and 102 L for raw water at a flow rate of 0.4-2 L min(-1), 95 and 107 L for treated water at a flow rate of 1.5-2.2 L min(-1). Limit of quantitation (LOQ) was a function of sample volume and it decreased with increasing sample volume. The LOQ of PCDD/Fs in raw waters analyzed by this method was 3-11 times lower than that described using large-size disk-type solid phase extraction (SPE) method. The LOQ of PCDD/F congeners in raw water and treated water were 0.022-3.9 ng L(-1) and 0.018-0.74 ng L(-1), respectively. Octachlorinated dibenzo-p-dioxin (OCDD) was found in some raw water samples, while their concentrations were well below the tentative criterion set by the Japanese Environmental Ministry for drinking water. OCDD was below the LOQ in the treated drinking water.     

工业废气中丙酸和丙烯酸的测定

建立了用离子色谱法测定有组织废气和无组织废气中丙酸和丙烯酸的新方法,常规无机阴离子对此没有干扰。对实际废气样品进行分析,丙酸、丙烯酸的回收率分别为91.2%~106%、92.0%~104%。该方法分析速度快,所需样品量少,且无需复杂的前处理过程,简便、灵敏、可靠。     

Determination of ethanolamine,ethylene glycol and triethylene glycol by ion chromatography for laboratory and field biodegradation studies

The determination of alkanolamines and glycols in groundwater and subsurface environments is essential for environmental assessment, remediation and monitoring for selected industrial sites. Monoethanolamine (MEA), ammonium, sodium, magnesium and calcium detection was performed using cation exchange chromatography (IC) with suppressed conductivity detection. Acetate, chloride, nitrite, nitrate, phosphate, sulfate and oxalate were monitored employing anion exchange chromatography with suppressed conductivity. Detection of ethylene glycol (MEG) and triethylene glycol (TEG) and ethanol was carried out using ion exclusion chromatography with pulsed amperometric detection. Effective determination of MEA, MEG and TEG in complex groundwater matrices without compound transformation offered improved monitoring capabilities. This study presents robust analytical tools for MEA, MEG and TEG determination in biodegradation studies. Using ion chromatography offered significant advantages for the analyses of groundwater samples and laboratory bioreactor monitoring.     

固体废物氰化物总量和浸出毒性测定方法的比较

中国现行的固体废物氰化物总量和氰化物浸出毒性的分析方法存在缺陷,不便于广泛指导监测工作,笔者优化了固体废物氰化物测定的前处理方法,明确了固体废物氰化物总量、氰化物浸出毒性测定时的样品粒径、浸提方法和消解方法,建立了容量法、分光光度法、流动注射法测定固体废物氰化物总量和浸出毒性的方法,并与标准方法（离子色谱法）进行比较。实验结果表明：容量法、分光光度法、流动注射法测定结果与离子色谱法无显著差异,3种方法测定固体废物氰化物总量加标回收率为80.5%~102%,平行样测定相对标准偏差为3.0%~6.9%,3种方法测定固体废物氰化物浸出毒性加标回收率为80.1%~107%,平行样测定相对标准偏差为7.8%~9.5%,3种方法测定结果精密度和准确度良好,均能够满足固体废物氰化物总量和氰化物浸出毒性的测定要求。其中容量法、分光光度法由于其仪器设备简单、操作简便,可用于突发环境事件应急监测等情况下固体废物氰化物的测定。但容量法检出限较高,不能满足评价标准较低的分析测试工作要求,离子色谱法、分光光度法和流动注射法检出限均能满足一般分析测试要求。     

Characterization and diurnal variation of size-resolved inorganic water-soluble ions at a rural background site

Water-soluble inorganic ions in aerosol samples have been studied. The sample collection took place during summer in 2003 at a European background site which is operating within the framework of the European Monitoring and Evaluation Program. Gent type PM10 stacked filter unit (SFU) samplers were operated in parallel on a day and night basis to collect particles in separate coarse (2.0-10 microm) and fine (<2.0 microm) size fractions. Particulate masses were measured gravimetrically; the filters from one of the SFU samplers were analyzed by particle-induced X-ray emission spectrometry (PIXE) and instrumental neutron activation analysis (INAA). Filters from the other SFU sampler were analyzed by ion chromatography (IC) for major inorganic anions (MSA-, NO2(-), NO3(-), Cl-, Br-, SO4(2-), oxalate) and cations (Na+, K+, NH4(+), Mg2+, Ca2+). The water-soluble inorganic ions measured were responsible for 44% and 16% of the total fine and coarse particulate mass, respectively. In the fine size fraction, the main ionic components were SO4(2-) and NH4(+) accounting for about 90% of fine ionic mass. In the coarse fraction the main ionic components were Ca2+ and NO3(-), followed by SO4(2-). Significant day and night difference in the mass concentrations was observed only for fine NO3(-). The molar ratios of fine NH4(+) to SO4(2-) indicated their complete neutralization to (NH4)2SO4. According to the cation-to-anion ratios the coarse particles were alkaline, while the fine particles were slightly acidic or neutral. By comparing the corresponding concentrations obtained from PIXE/INAA and IC, we determined the water-extractable part of the individual species. We also investigated the effect of long-range transported air masses on the local air concentrations, and we found that the air quality of this background monitoring station was affected by regional pollution sources.     

The role of Raman spectroscopy in the analytical chemistry of potable water

Advances in instrumentation are making Raman spectroscopy the tool of choice for an increasing number of chemical applications. For example, many recalcitrant industrial process monitoring problems have been solved in recent years with in-line Raman spectrometers. Raman is attractive for these applications for many reasons, including remote non-invasive sampling, minimal sample preparation and tolerance of water. To a lesser extent, Raman spectroscopy is beginning to play a significant role in environmental analysis for the same reasons. At present, the environmental applications typically apply only to the most contaminated situations due to the still relatively high limits of detection. However, some emerging sampling technologies hold out the promise that Raman may soon be more widely applicable to the analytical chemistry of potable water. Herein we discuss these recent advances, summarize some examples of environmental applications to aqueous systems and suggest avenues of future developments that we expect to be most useful for potable water analysis. Also, a simplified, but detailed, theory of normal Raman scattering is presented. While resonance-enhanced Raman spectroscopy, surface-enhanced Raman spectroscopy and non-linear Raman techniques are briefly discussed, their theories and instrumental configurations are not addressed. Also, this article deals primarily with the modern dispersive Raman experiment (as opposed to the Fourier transform Raman experiment), because it seems most suited for potable water analysis. The goal of this article is to give the environmental scientist with no specialized knowledge of the topic just enough theory and background to evaluate the utility of this rapidly developing analytical tool.     

Ascorbic acid treatment to reduce residual halogen-based oxidants prior to the determination of halogenated disinfection byproducts in potable water

Treatment of potable water samples with ascorbic acid has been investigated as a means for reducing residual halogen-based oxidants (disinfectants), i.e. HOCl, Cl2, Br2 and BrCl, prior to determination of EPA Method 551.1A and 551.1B analytes. These disinfection byproducts include certain haloalkanes, haloalkenes, haloethanenitriles, haloaldehydes, haloketones and trichloronitromethane. When used as a dehalogenating agent immediately before analysis, only one analyte, 2,2,2-trichloroethanediol (chloral hydrate), is significantly decomposed. Ascorbic acid is superior to thiosulfate and sulfite as it does not destroy trichloroethanenitrile (trichloroacetonitrile), trichloronitromethane (chloropicrin) or dibromoethanenitrile (dibromoacetonitrile). Unlike ammonia or amines, it is not nucleophilic and cannot form hemiaminals (carbinolamines) with carboxaldehydes and ketones. Ascorbic acid treatment can rapidly consume (reduce) large amounts of active (oxidizing) halogen compounds, producing only inorganic halides and dehydroascorbic acid and not additional halogenated organic molecules.     

Flow-injection analysis with fluorescence detection for the determination of trace levels of ammonium in seawater

A method using flow-injection, gas-diffusion, derivatisation and then fluorescent detection has been established for ammonium ion determination in seawater. The fluorescent derivative formed by reacting ortho-phthaldialdehyde (OPA) and sulfite with ammonia gives high sensitivity while removing potential interferences. This is required to measure the low concentrations of ammonium often seen in the open ocean. The experimental conditions (flow-rate, reagent concentrations, membrane configurations, etc.) were manipulated to improve performance. For a sample throughput of 30 samples h(-1), the limit of detection was 7 nM, the coefficient of variation was 5.7% at 800 nM, and the calibration curve was linear to at least 4 micromol L(-1). Interferences were minimised by a gaseous diffusion step. Volatile small molecular-weight amines as interferents were discriminated against by this method. They neither passed through the membrane as efficiently as ammonia, nor reacted as readily with OPA when sulfite was the reductant. Contamination by ammonia from laboratory and shipboard sources complicates application of the method to natural waters, especially measurement of low concentrations (<100 nM) in open-ocean waters. Steps to overcome contamination are described in detail. Some results are presented for ammonium determination in Southern Ocean and Huon Estuary (Tasmania) waters.     

Deterioration of coastal groundwater quality in Island and mainland regions of Ramanathapuram District, Southern India

A study was carried out in the Island and mainland regions of Ramanathapuram District to characterize the physico-chemical characteristics of 87 groundwater samples in Island and 112 groundwater samples in mainland which include pH, EC, TDS, salinity, total alkalinity, calcium hardness, magnesium hardness, total hardness, chloride and fluoride. Heavy inorganic load in majority of the groundwater samples has been estimated due to the salinity, TDS, TH and chloride beyond the threshold level which substantiates the percolation of sea water into the freshwater confined zones. Although the groundwater sources are available in plenty, the scarcity of potable water is most prevalent in this coastal area. The Water Quality Index (WQI) and Langeleir Saturation Index (LSI) have also been calculated to know the potable and corrosive/incrusting nature of the water samples. The statistical tools such as principal component analysis, box plots and correlation matrix have also been used to explain the influence of different physico-chemical parameters with respect to one another among the groundwater samples. The percentage of groundwater samples in mainland was more than that in Island with respect to the acceptable limit of WHO drinking standard, especially in TDS, CH, TH and chloride but the converse is observed in the case of fluoride. About 8 % of the mainland aquifers and 42 % of Island aquifers were identified to have fluoride greater than 1.5 mg/l. The signature of salt-water intrusion is observed from the ratio of Cl/CO ₃ ^2? ?+?HCO₃ and TA/TH. A proper management plan to cater potable water to the immediate needs of the people is to be envisaged.     

食品生产企业周边空气中的异味监测

简述了食品生产企业产生的异味无机物、有机物的种类,指出其异味主要来源于食品加工、原料贮存以及废物处理等环节,分析了异味物质的产生机理。介绍了空气中异味物质的监测方法包括,嗅辨法、气相色谱-质谱联用法、傅里叶红外光谱法以及气相色谱/气相色谱-质谱与嗅闻联用法等,及其适用性,以及测定结果的评价方法。     

气相分子吸收光谱法在海水无机氮测定中的适用性研究

为探究气相分子吸收光谱法在海水无机氮测定中的适用情况,在检出限的10～20倍、30～50倍、50～100倍3个浓度范围内开展了准确度、加标回收率和方法比对试验。结果表明,采用气相分子吸收光谱法测定海水亚硝酸盐氮(0～0.100 mg/L)、硝酸盐氮(0～0.400 mg/L)、氨氮(0～0.200 mg/L)时,标准曲线均具有很好的线性,线性拟合度均在0.999 3以上,检出限依次为0.000 8、0.004、0.004 mg/L,且该方法不具有盐效应,适用于海水样品的检测。当样品浓度太低时,气相分子吸收光谱法测定结果的准确度较低,因此,建议仅在亚硝酸盐氮浓度高于0.030 mg/L、硝酸盐氮浓度高于0.100 mg/L、氨氮浓度高于0.090 mg/L时使用该方法,对应的海域为河口及近岸等无机氮含量较高的海域。此外,为保证测定结果的准确度,每个样品需平行测定2～3次。     

Identification of Characteristic Regions and Representative Stations: A Study of Water Quality Variables in the Kattegat

Gradients in nutrient distributions and the effects of eutrophication are common features in most coastal marine areas. These structures occur in aquatic systems due to spatial differences in hydrography, nutrient loading and key biogeochemical processes. Two statistical methods, cluster analysis and probability mapping, have been used in the present study to determine characteristics and patterns in water quality variables. Combined, these two methods provide a useful tool to statistically determine spatial homogeneity and representativity of areas and stations. A case study is presented here in which water quality variables (salinity, dissolved inorganic nitrogen, dissolved inorganic phosphorus and chlorophyll) in surface waters of the Kattegat are analysed for the time period 1993-1997. It was found that morphology, the proximity to sources of nutrient loading from land, nutrient uptake and the infrequent water exchange between the Baltic Sea in the south and the Skagerrak in the north all contribute to create distinct regions of water quality. Regions with concentrations significantly different from the overall mean are identified. In addition to identification of regions with similar characteristics, representative stations (as well as not representative stations) for the respective regions were made. This type of information can be used to design new or revise old monitoring programs.     

Performance of methods for measurement of exposure to inorganic acids in workplace air

BGIA has organised round robins for the analysis of samples of inorganic acids in workplace air for a number of years. Test samples of the volatile acids HCl and HNO(3) are collected from a standard atmosphere and samples of the non-volatile acids H(3)PO(4) and H(2)SO(4) are prepared by spiking filters with acid solution. The last two round robins have also covered the sampling of volatile acids, with up to 15 "active" participants able to visit the test facility in Dresden and take samples themselves. For other "passive" participants, BGIA takes samples from the same atmosphere. The acid concentrations generated lie between 0,1 and 1 times the German limit values for HCl and HNO(3). The results for the last round robin showed no significant difference between the performance of the "active" and "passive" participants. The participant means were in good agreement with the theoretical concentrations and the quality control measurements. For "active" participants RSDs were between 7% and 14% and for all participants between 8% and 16%. The round robin for the non-volatile acids showed similar results. The participant means were again in excellent agreement with the quality control measurements and RSDs were between 12% and 15%. The BGIA round robins have demonstrated the proficiency of laboratories measuring exposure to inorganic acids in air. However, concerns remain about the performance of published methods. It has shown that the sampling efficiency of sorbent tubes falls off with increasing particle size and hence silica gel tube methods may give low results for acid mists. Another issue with silica gel tubes is that a substantial proportion of the sample can be collected on the glass wool plugs that retain the sorbent. This can be up to 50% for HCl and 100% for HNO(3). Hence, low results may be obtained if the glass wool plugs are discarded. Similarly, methods for volatile inorganic acids that use a pre-filter to remove particulates usually overlook the fact that the acids can react with co-particulate matter on the pre-filter. Low recoveries in the range 30%-50% have been found when sampling HCl through filters loaded with potential interferents. Finally, particulate salts interfere with filter sampling methods for non-volatile inorganic acids. A two-part International Standard is in preparation for inorganic acids by ion chromatography and the issues discussed above are being taken into consideration during its development.     

梯度淋洗离子色谱法测定饮用水中6种阴离子

采用离子色谱法同时测定饮用水中F-、Cl-、Br-、NO3-、SO24-、PO34-等6种阴离子,水样经0.22μm滤膜过滤,自动淋洗发生器产生20 mmol/L～40 mmol/L KOH淋洗液梯度洗脱,在流量0.25 mL/min条件下采用IonPac AG19保护柱和IonPac AS19分离柱分离和定量。方法线性良好,6种阴离子的检出限为0.005 mg/L～0.057 mg/L,标准溶液平行测定6次,测定值的RSD在0.5%～2.2%之间,水样加标回收率在83%～106%之间。